Nonaqueous electrolytic solution and nonaqueous electrolytic solution secondary battery using same

Abstract

The present invention relates to a nonaqueous electrolytic solution for use in a nonaqueous electrolytic solution secondary battery that comprises a negative electrode and a positive electrode capable of storing and releasing metal ions, and a nonaqueous electrolytic solution, wherein the nonaqueous electrolytic solution contains the specific compounds (A) and (B).

1 . A nonaqueous electrolytic solution for use in a nonaqueous electrolytic solution secondary battery that comprises a negative electrode and a positive electrode capable of storing and releasing metal ions, and a nonaqueous electrolytic solution,
 wherein the nonaqueous electrolytic solution contains the following (A) and (B):   (A) a compound that does not have an aliphatic substituent having an unsaturated bond but has a Si—Si bond;   (B) at least one compound selected from the group consisting of a carbonate ester having an unsaturated bond, a compound represented by the following general formula (1), a compound having a S═O group, a compound having an NCO group, monofluorophosphate, difluorophosphate, fluorosulfonate, and an imide salt,   
       
         
           
           
               
               
           
         
         [wherein M represents a transition metal, an element of group 13, 14, or 15 of the periodic table, or a hydrocarbon group of 1 to 6 carbon atoms that may have a heteroatom, where when M represents a transition metal, or an element of group 13, 14, or 15 of the periodic table, Z a+  is a metal ion, a proton, or an onium ion, a represents 1 to 3, b represents 1 to 3, 1 represents b/a, m represents 1 to 4, n represents 1 to 8, t represents 0 to 1, p represents 0 to 3, q represents 0 to 2, and r represents 0 to 2, and where when M is a hydrocarbon group of 1 to 6 carbon atoms that may have a heteroatom, Z a+  does not exist, and a=b=1=n=0, m=1, t represents 0 to 1, p represents 0 to 3, q represents 0 to 2, and r represents 0 to 2, 
         R 1  represents a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms that may have a heteroatom, or X 3 R 4  (where R 1  that exists in number n may bind to one another to form a ring), R 2  represents a direct bond, or a hydrocarbon group of 1 to 6 carbon atoms that may have a heteroatom, X 1 , X 2 , and X 3  each independently represents O, S, or NR S , and R 3 , R 4 , and R 5  each independently represent hydrogen, a hydrocarbon group of 1 to 10 carbon atoms that may have a heteroatom (a plurality of R 3  and R 4  may bind to one another to form a ring), and Y 1  and Y 2  each independently represent C, S, or Si, wherein, when Y 1  or Y 2  is C or Si, q or r is 0 or 1, and, when Y 1  or Y 2  is S, q and r each are 2]. 
       
     
     
         2 . The nonaqueous electrolytic solution according to  claim 1 , wherein the compound having a S═O group is a compound represented by the following general formula (2), 
       
         
           
           
               
               
           
         
         (wherein L represents an optionally substituted organic group with valence number a, R 4  represents a halogen atom, a hydrocarbon group of 1 to 4 carbon atoms, or an alkoxy group, a is an integer of 1 or more, and, when a is 2 or more, a plurality of R 4  may be the same or different, and wherein R 4  and L may bind to each other to form a ring. 
       
     
     
         3 . The nonaqueous electrolytic solution according to  claim 1 , wherein the compound having an NCO group is a compound represented by the following general formula (3), 
       
         
           
           
               
               
           
         
         (wherein R 5  represents an organic group of 1 to 20 carbon atoms that may have a branched structure or an aromatic group, and Q represents a hydrogen atom or an NCO group). 
       
     
     
         4 . The nonaqueous electrolytic solution according to  claim 2 , wherein at least one compound selected from the group consisting of the carbonate ester having an unsaturated bond, the compound represented by the general formula (1), the compound represented by the general formula (2), and the compound represented by the general formula (3) is at least one compound selected from the group consisting of vinylene carbonate, vinylethylene carbonate, ethynylethylene carbonate, methylpropargyl carbonate, dipropargyl carbonate, lithium bis(oxalate)borate, lithium difluorooxalateborate, lithium tris(oxalate)phosphate, lithium difluorobis(oxalate)phosphate, lithium tetrafluorooxalatephosphate, ethynylethylene sulfate, propynyl vinyl sulfonate, and hexamethylene diisocyanate. 
     
     
         5 . The nonaqueous electrolytic solution according to  claim 1 , wherein at least one compound selected from the group consisting of the monofluorophosphate, the difluorophosphate, the fluorosulfonate, and the imide salt is at least one compound selected from the group consisting of lithium monofluorophosphate, lithium difluorophosphate, lithium fluorosulfonate, LiN(FSO 2 ) 2 , LiN(CF 3 SO 2 ) 2 , and LiN(C 2 F 5 SO 2 ) 2 . 
     
     
         6 . A nonaqueous electrolytic solution for use in a nonaqueous electrolytic solution secondary battery that comprises a positive electrode capable of storing and releasing metal ions, a negative electrode that contains a carbonaceous material, and a nonaqueous electrolytic solution,
 wherein the nonaqueous electrolytic solution contains a compound that does not have an aliphatic substituent having an unsaturated bond but has a Si—Si bond, and a carbonate ester having a halogen atom.   
     
     
         7 . The nonaqueous electrolytic solution according to  claim 6 , wherein the carbonate ester having a halogen atom is at least one compound selected from monofluoroethylene carbonate, 4,4-difluoroethylene carbonate, and 4,5-difluoroethylene carbonate. 
     
     
         8 . The nonaqueous electrolytic solution according to  claim 1 , wherein the compound that does not have an aliphatic substituent having an unsaturated bond but has a Si—Si bond is a compound represented by the following general formula (4). 
       
         
           
           
               
               
           
         
         (wherein A 1  to A 6  may be the same or different, and represent a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 10 carbon atoms that may have a heteroatom, or an optionally substituted hydrogen silicide group of 1 to 10 silicon atoms, and wherein A 1  to A 6  may bind to one another to form a ring, where none of A 1  to A 6  is an aliphatic substituent having an unsaturated bond). 
       
     
     
         9 . The nonaqueous electrolytic solution according to  claim 1 , wherein the compound that does not have an aliphatic substituent having an unsaturated bond but has a Si—Si bond is at least one selected from the group consisting of hexamethyldisilane, hexaethyldisilane, 1,2-diphenyltetramethyldisilane, and 1,1,2,2-tetraphenyldisilane. 
     
     
         10 . The nonaqueous electrolytic solution according to  claim 1 , which comprises the compound that does not have an aliphatic substituent having an unsaturated bond but has a Si—Si bond in an amount of 0.01 mass % or more and 10 mass % or less. 
     
     
         11 . A nonaqueous electrolytic solution secondary battery that comprises a carbon-based negative electrode and a positive electrode capable of storing and releasing metal ions, and a nonaqueous electrolytic solution,
 wherein the nonaqueous electrolytic solution is the nonaqueous electrolytic solution of  claim 1 .   
     
     
         12 . The nonaqueous electrolytic solution according to  claim 3 , wherein at least one compound selected from the group consisting of the carbonate ester having an unsaturated bond, the compound represented by the general formula (1), the compound represented by the general formula (2), and the compound represented by the general formula (3) is at least one compound selected from the group consisting of vinylene carbonate, vinylethylene carbonate, ethynylethylene carbonate, methylpropargyl carbonate, dipropargyl carbonate, lithium bis(oxalate)borate, lithium difluorooxalateborate, lithium tris(oxalate)phosphate, lithium difluorobis(oxalate)phosphate, lithium tetrafluorooxalatephosphate, ethynylethylene sulfate, propynyl vinyl sulfonate, and hexamethylene diisocyanate. 
     
     
         13 . The nonaqueous electrolytic solution according to  claim 6 , wherein the compound that does not have an aliphatic substituent having an unsaturated bond but has a Si—Si bond is a compound represented by the following general formula (4). 
       
         
           
           
               
               
           
         
         (wherein A 1  to A 6  may be the same or different, and represent a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 10 carbon atoms that may have a heteroatom, or an optionally substituted hydrogen silicide group of 1 to 10 silicon atoms, and wherein A 1  to A 6  may bind to one another to form a ring, where none of A 1  to A 6  is an aliphatic substituent having an unsaturated bond). 
       
     
     
         14 . The nonaqueous electrolytic solution according to  claim 6 , wherein the compound that does not have an aliphatic substituent having an unsaturated bond but has a Si—Si bond is at least one selected from the group consisting of hexamethyldisilane, hexaethyldisilane, 1,2-diphenyltetramethyldisilane, and 1,1,2,2-tetraphenyldisilane. 
     
     
         15 . The nonaqueous electrolytic solution according to  claim 6 , which comprises the compound that does not have an aliphatic substituent having an unsaturated bond but has a Si—Si bond in an amount of 0.01 mass % or more and 10 mass % or less. 
     
     
         16 . A nonaqueous electrolytic solution secondary battery that comprises a carbon-based negative electrode and a positive electrode capable of storing and releasing metal ions, and a nonaqueous electrolytic solution,
 wherein the nonaqueous electrolytic solution is the nonaqueous electrolytic solution of  claim 6 .